Basic dyes of the naphtholactam series

ABSTRACT

Basic dyes of the naphtholactam series derived from an Nalkoxycarbonylethyl naphtholactam and an N-substituted aniline. They dye anionically modified textile material such as polyesters or acrylonitrile polymers blue shades.

Unified States Patent [191 Baumarm et a1.

[ Aug. 28, 1973 BASIC DYES OF THE NAPHTHOLACTAM SERIES [75] Inventors: Hans Baumann, Ludwigshafen;

Andreas Einwlller, Mannheim, both [21] App]. No.: 160,908

[52] U.S. Cl..... 260/326.3, 260/247.2 B, 260/247.1, 260/293.6l, 260/310 D, 260/41, 8/7, 8/12,

8/55, 106/22 [51] Int. Cl C07d 27/72 [58] Field of Search 260/326.3, 310 D,

[56] References Cited UNITED STATES PATENTS 3,649,645 3/1972 Yamada e l al 260/32662 Primary Examiner-Joseph A. Narcavage An0rney-Johnston, Root, O'Keefe, Keil, Thompson & Shurtleff 5 7 1 ABSTRACT Basic dyes of the naphtholactam series derived from an N-alkoxycarbonylethyl naphtholactam and an N- substituted aniline. They dye anionically modified textile material such as polyesters or acrylonitrile polymers blue shades.

4 Claims, No Drawings BASIC DYES OF THE NAPI-ITHOLACTAM SERIES The invention relates to basic dyes having the general formula (I):

where R denotes unsubstituted or substituted alkyl;

R denotes unsubstituted or substituted alkyl, aralkyl or aryl;

R denotes hydrogen or unsubstituted or substituted alkyl;

R and R together with the nitrogen atom denote the radical of a heterocyclic ring; and

A" denotes an anion and where the ring of the naphthalene may bear, as substituents, chlorine or bromine or unsubstituted or substituted sulfonamido.

Specific examples of R are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, B-chloroethyl, B-hydroxyethyl, B-hydroxypropyl, vS-hydroxybutyl and 2-hydroxy-3-chloropropyl.

Examples of substituents R are: methyl, ethyl, propyl, butyl, B-hydroxyethyl, Bacetoxyethyl, B-cyanoethyl, fi-chloroethyl, benzyl, phenylethyl, phenyl, ethoxyphenyl, and methoxyphenyl.

Examples of R are: methyl, ethyl, propyl, butyl, B-hydroxyethyl and B-cyanoethyl.

Anions A may be simple or complex and are derived from inorganic or organic acids. Specific examples include chloride, bromide, sulfate, nitrate, methosulfate, ethosulfate, benezenesulfonate, toluenesulfonate, formate, acetate, tetrafluoborate, and particularly tetrachlorozincate.

Particular industrial importance attaches to dyes having the general formula (Ia):

II i) where 2 hydroxyethylsulfonamide, N-ethyl-N-B-hydroxyethylsulfonamide, N-butyl-N-B-hydroxyethylsulfonamide and N,N-di-B-hydroxyethylsulfonamide.

The dyes having the formula (I) may be prepared by reaction of a naphtholactam having the general formula (ll):

with an amine having the general formula (III):

(III) in the presence of a water-eliminating condensing agent. R, R and R have the meanings given above and the rings A may bear the specified substituents.

Examples of water-eliminating condensing agents are: PCl PCI POCl POBr SOCl SO CI AlCl ZnCl BF and mixtures of these compounds. The reaction may be carried out with or without a solvent. If desired inert solvents may be added such as hydrocarbons or chlorohydrocarbons, for example benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, chloroform, ethylene chloride and 1,2- dichloropropane.

Examples of components having the formula (II) are:

N-B-carbomethoxyethylnaphtholactam N-B- carboethoxyethylnaphtholactam, N-B- carboisopropoxyethylnaphtholactam. N-B- carbobutoxyethylnaphtholactam, N-B- carboisobutoxyethylnaphtholactam N-B- carbomethoxyethyl-4-chloronaphtholactam N-B-carbomethoxyethylnaphtholactam, N-B-carboethoxyethylnaphtholactam N-B-carboisopropoxyethylnaphtholactam, N-B-carbobutoxyethylnaphtholactam N-B-carboisobutoxyethylnaphtholactam N-B-carbomethoxyethylA-chloronaphtholactam, N-B-carbomethoxyethyl-4-bromonaphtholactam N -B-carbomethoxyethyl-4-dimethylsulfonamidonaphtholactam, N-B-carbomethoxyethylA-diethylsulfonamidonaphtholactam, N-B-carbomethoxyethyl-4- sulfopiperididonaphtholactam, N-B-carbomethoxyethyl-4-sulfomorpholidonaphtholactam, N-B-carboxymethoxyethyl-4-sulfopyrrolididonaphtholactam, N-B-carboethoxyethyl-4-chloronaphtholactam N-B-carboethoxyethyl-4-bromonaphtholac tam N-B-carboethoxyethyl-4-dimethylsulfonamidonaphtholactam N-fi-carboethoxyethyl-4-dicthylsulfonamidonaphtholactam N-fi-carboethoxyethyltsulfopiperididonaphtholactam,

N-B-carbobutoxyethyl-4-sulfomorpholidonaphtholactam N-B-carbobutoxyethyl-4-sulfopyrrolididonaphtholactam,

N-B-carbobutoxyethyl-4-chloronaphtholactam, N-B-carbobutoxyethyl-4-bromonaphtholactam, N-B-carbobutoxyethyl-4-dimethylsulfonamidonaphtholactam, N-B-carbobutoxyethyl-4-diethylsulfonamidonaphtholactam, N-fl-carbobutoxyethylisulfopiperididonaphtholactam, N-/3-carbobutoxyethyl-4-sulf0morpholidonaphtholactam, N-B-carbobutoxyethyl-4-sulfopyrrolididonaphtholactam, N-B-carboisobutoxyethyl-4-chloronaphtholactam, N-B-isobutoxyethyl-4bromonaphtholactam, N-,8-carboisobutoxyethyl-4-dimethylsulfonamidonaphtholactam, N-B-carboisobutoxyethyl-4-diethylsulfonamidonaphtholactam, N-B-carboisobutoxyethyl-4-sulfopiperididionaphtholactam, N-B-carboisobutoxyethyl-4-sulfomorpholidonaphtholactam, N-B-carboisobutoxyethyl-4-sulfopyrrolididonaphtholactam, and the compounds havingthe formulae:

The abovementioned compounds having the formula (ii) are obtained by reaction of acrylic esters with naphtholactams or naphtholactam derivatives, preferably in a solvent such as N-methylpyrrolidone, dioxane, dimethylformamide, dimethylsulfoxide or tetramethyleneurea, in the presence of basic condensing agents such as sodium methylate, sodium ethylate, sodium formate, sodium acetate, postassium methylate, potassium ethylate, potassium formate, or potassium acetate.

Examples of components having the formula (III) are: N,N-dialkylanilines, diphenylamine and N- alkyldiphenylamines which may bear alkyl, acylamino or alkoxy radicals as substituents in the aryl radical, and moreover l-phenylpyrazolones which may bear alkyl and aryl radicals in the 3 and 5 positions, and also N-phenylmorpholine.

The following specific examples are given:

dimethylaniline, diethylaniline, dibutylaniline, N43- cyanoethyl-N-methylaniline, N-B-cyanoethyl-N- ethylaniline, N-B-cyanoethyI-N-butylaniline, N-B- hydroxyethyl-N-ethylaniline, N,N-di-B- hydroxyethylaniline, N-benzyl-N-ethylaniline, N-B- phenylethyl-N-B-cyanoethylaniline, diphenylamine, N- methyldiphenylamine, N-ethyldiphenylamine, N- methyl-4-ethoxydiphenylamine, I pyrazoline-A-Z, l,3,S-triphenylpyrazoline-A-Z, phenyl-3,5,S-trimethylpyrazoline-A-Z and phenylmorpholine.

The dyes having the formula (I) are suitable for dyeing cotton that has been treated with tannic acid, leather, paper, inks, including ball point pen inks, and particularly for dyeing and/or printing anionically modified acrylonitrile polymer or polyester materials or textiles.

The water-soluble blue dyes give light fast and wet fast dyeings on acrylonitrile polymer textile material. The new dyes exhibit a tinctorially valuable bathochromic shift as compared with prior art dyes of this type bearing a methyl or ethyl group on the nitrogen atom of the naphtholactam.

The following Examples illustrate the invention. Statements as to parts and percentages are by weight unless otherwise stated.

EXAMPLE 1 25.5 parts of N-B-carbomethoxyethylnaphtholactam, 8 parts of zinc chloride, 125 parts of ethylene chloride and 45 parts of phosphorus oxychloride are heated to C while stirring. l2.l parts of dimethylaniline is dripped in at this temperature and the temperature is maintained for 8 hours at C. The whole is poured into water and the solvent is distilled off. After neutralization has been effected with sodium acetate and a solution of common salt has been added, a good yield of the dye having the constitution:

is precipitated. It dyes polyacrylonitrile fibers fast blue shades.

N-B-carbomethoxyethylnaphtholactam can be prepared as follows: 169 parts of naphtholactam is dissolved in 400 parts of dimethylformamide, parts of potassium acetate is added and the solution is then heated to 70C. 160 parts of methyl acrylate is dripped in at this temperature in the course of 20 minutes and after the addition is completed the temperature is raised to C and the whole is stirred for another 8 hours. The reaction mixture, after it has cooled, is

l-phenyl-E-methyl; l-

EXAMPLE 2 is isolated by a conventional method. It dyes acrylonitrile polymer cloth very fast greenish blue shades.

EXAMPLE 3 A mixture of 26.9 parts of N-B-carboethoxyethylnaphtholactam, 8 parts of zinc chloride, 75 parts of phosphorus oxychloride and 100 parts of benzene is kept at 60C for 20 minutes. parts of diethylaniline is then dripped in and the whole is stirred at 80C for 8 hours. The dye having the constitution:

precipitates out from the reaction mixture and can be isolated in a good yield by suction filtration followed by washing with saturated common salt solution. The dye is suitable for dyeing and printing polyacrylonitrile in fast blue shades.

EXAMPLE 4 36.2 parts of N-B-carbomethoxyethylnaphtholactam- 4-dimethylsulfonamide, 8 parts of zinc chloride, parts of phosphorus oxychloride and 120 parts of l,2- dichloropropane are kept at C for 30 minutes. 12.1 parts of dimethylaniline is dripped in, the temperature is raised to 85C and the whole is stirred for another 8 hours. It is then poured into water and the solvent is distilled off. About 5 parts of activated carbon is added to the mixture and the acid aqueous solution is heated to C and filtered. When the filtrate is neutralized with sodium acetate and common salt solution is added, the dye having the formula:

is precipitated. lt dyes polyacrylonitrile fibers fast blue shades.

In an analogous manner to that described, dyes having the formula:

l A X characterized in the following Table by the substituents indicated are obtained.

Shade of d elng on polyacrylomin-11v Example N0.

Blue iolmv CzHa 16 CH: H

Blue. 0 (3:11

20 CH3 B1, CQEIlEN Same as above Shade of dysing on if x Y fi i$"' 20 c113 /W /CH; D0.

CzH|CN 3O .4 CH; Same as above Cal-15 Do.

C1H4CN 31 CH; CzH5 Do SOzN H N CzH5 32 CH3 Same as above C4Ho D0.

33 CgH H CH; D-

CHa

a4 CzHs H 04H Do.

C|H9 35 CzH H C2H4OH Blue violet.

36 02115 H Do.

37 C2115 Cl CzH5 Blue.

38 C 113 Cl CH3 D0.

CQHlCN CzHs CH3 CH3 D0.

S02-N N CH: CHa

40 C2115 Same as above C H4Cl D0.

CgH

41 mam H c113 Do.

42 A. n-C4Hs H CzHs Do.

0:11 43 n-C4Hn H 0211401 Blue violet.

Cal-I5 H n-(flln II N Blue.

CH CH3 45 V .4 n-Cflh (l CH D0.

Shade of E l dyleing Oil xamp e p yacr 0- No. X Y nitrile 3 46 n-CaHH Cl C Hs D0.

47 n-Crlh Cl D0.

CzHA

CZH4CN 48 l'l-CII'IQ CgHs /C:H DO.

' s oi-N N\ CzHs Cz s 49 nC H9 Same as above /CH40H Do.

CzHs

50 n-CiHg do \0 Do.

51 l-CgHn H CH3 D0- 52 i-C H1 H CH Blue violet.

CQHACN 53 i-Cdh H CLIH5 13111 CzHa 54 i-C3H7 H C H Blue violet.

CQHlCN 55 i-C H1 H CgHs Blue.

GzHs

. 45 r We claim: N v N 1. A basic dye having the formula w N or N lt K in which R is alkyl of from one to four carbon atoms, hydroxyalkyl of from two to four carbon atoms, B-chloro- X is hydrogen, chlorine, bromine or a radical of the forand A is an anion represented by chloride, bromide, sulfate, nitrate, methosulfate, ethosulfate, benzenesulfonate, toluenesulfonate, formate, acetate, tetrafluoborate or tetrachlorozincate.

2. A basic dye having the formula I It m n 13 }N/ H -7 I I u 11 3. The dyes having the formula CIIiS o-c-c,n.-r-i N/ i In n -s I 1 I -ZnCl in which Z is methyl or ethyl.

4. The dyes having the formula lz c w Br 2 in which Z is methyl or ethyl.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,755, 353

DATED August 28, 1973 INVENTOR(S) Hans Baumann and Andreas Einwiller It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the heading insert--[30] Foreign Application Priority, July 23, 1970, Germany, P 20 36 504.2-.

Signed and Sealed this A ttest:

RUTH C. MASON C. MAR Allestr'ng Offi SHALL DANN ommissr'nner uj'PaIents and Trademarks UNITED STATES PATENT OFFICE CTEN CERTEFEQATE or to Patent No. 5353 Dated August 28,. 1973 Inventor(s) i 1 1pm O It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, l1ne 38, benezenesulfonate" should read benzenesnlfonate Column 2, lines- 33-38, delete lines 33-38.

Column 4, line 2, "postassium" should read potassium Signed and sealed this 8th day of October 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. 0. MARSHALL DANN Attesting Officer Commissioner of Patents FORM USCOMM-DC 60376-P69 9 (1.5 GOVERNMENT PRINTHIG OFFICE: I95!) 0"355334. 

2. A basic dye having the formula
 3. The dyes having the formula
 4. The dyes having the formula 